Failure of ESI Spectra to Represent Metal-Complex Solution Composition: A Study of Lanthanide-Carboxylate Complexes

Journal Article · Tue Jan 21 00:00:00 EST 2014 · Analytical Chemistry

DOI:https://doi.org/10.1021/ac401751r· OSTI ID:1225169

McDonald, Luther W.; Campbell, James A.; Clark, Sue B.

Electrospray ionization - mass spectrometry (ESI-MS) was used for the characterization of uranyl complexed to tributyl phosphate (TBP) and dibutyl phosphate (DBP). The stoichiometry of uranyl with TBP and DBP was determined, and the gas phase speciation was found to be dependent on the cone voltage applied to induce fragmentation on the gas phase complexes. To quantitatively compare the gas phase distribution of species to solution, apparent stability constants were calculated. With a cone voltage of 80V, the apparent stability constants for the complexes UO2(NO3)2•2TBP, UO2(NO3)2(H2O)•2TBP, and UO2(DBP)+ were determined. With a lower cone voltage applied, larger complexes were observed and stability constants for the complexes UO2(NO3)2•3TBP and UO2(DBP)42- were determined.

• Research Organization: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1225169
• Report Number(s): PNNL-SA-96226; WN0219080
• Journal Information: Analytical Chemistry, Vol. 86, Issue 2; ISSN 0003-2700
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

Related Subjects

Uranium
Solvent Extraction
PUREX
Actinides
Complexation
Nuclear Reprocessing
Electrospray Ionization